新型具三苯胺結構Polybenzoxazines之合成及電致變色特性與記憶體元件之應用研究

Abstract

本論文分為四個章節，第一章為總體序論，簡述benzoxazine、電致變色及高分子記憶體元件的發展。第二章包含了一系列新型具三苯胺結構polybenzoxazine，透過合成其前驅物再經熱交聯反應來製備，其中選用兩種二胺單體 (4,4'-diamino-4'-methoxytriphenylamine 和 N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxyphenyl)-1,4-phenylenediamine)做為反應物。第三章分析了一系列新型具三苯胺結構之polybenzoxazine及其前驅物的電致變色及高分子記憶體元件特性。第四章為結論。這系列新型具三苯胺結構polybenzoxazine及其前驅物之合成與基本特性、電化學性質、電致變色及高分子記憶體元件特性已被研究與比較。與傳統不具三苯胺結構之polybenzoxazine相比，此系列之新型polybenzoxazine表現較好的熱性質(Tg, 284-312 oC)。此外，含bisphenol A 結構之polybenzoxazine及其前驅物表現特殊的電致變色特性並在可見光及紅外光光譜吸收區域表現高對比的顏色變化，相較於三苯胺對應的聚醯胺，導入三苯胺衍生物進入polybenzoxazine前驅物可有效的增加氧化的階段及呈現多段電致變色的性質。此外，在高分子記憶體元件的部分，所有含強拉電子基團 (4,4׳-sulfonyldiphenol)的polybenzoxazine及其前驅物表現出揮發性SRAM的記憶體特性。具我們所知，直至目前為止，具三苯胺結構之polybenzoxazine及其前驅物應用於電致變色及高分子記憶體元件尚未被製備並且系統化探討，故本研究開創了polybenzoxazine的新應用領域。

This study has been separated into four chapters. Chapter 1 is general introduction of benzoxazine, electrochromism, and polymer memory. Chapter 2 includes a series of novel triarylamine (TPA)-based polybenzoxazines (PBs) which were prepared by the thermal-induced curing reaction of a series of novel PB precursors. Two diamines, 4,4'-diamino-4'-methoxytriphenylamine and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxyphenyl)-1,4-phenylenediamine, were used in this research, which were published by our group before. Chapter 3 includes the investigations of electrochromic and memory behaviors of novel PBs and PB precursors. Chapter 4 is conclusions. The synthesis, thermal properties, electrochemical properties, electrochromic properties, and memory behaviors of novel TPA-based PBs and PB precursors were investigated and compared. Comparing with the traditional PBs without TPA moieties, the novel TPA-based PBs exhibited more excellent thermal properties (Tg, 284-312 oC). In addition, the resulting TPA-based PBs and PB precursors containing bisphenol A (BPA) revealed interesting multi-electrochromic behavior with highly optical contrast both in visible and NIR region. Compared with their corresponding polyamides, these TPA-based PB precursors with BPA moiety not only showed lower oxidative potentials but also increased the oxidation stages due to the introduction of the TPA moieties. Besides, all the resulting polymer containing stronger electron-withdrawing group 4,4׳-sulfonyldiphenol (BPS) exhibited SRAM properties with longer retention time in terms of memory characteristics. To the best of our knowledge, this is the first time to explore and investigate the EC and memory behaviors of PB precursors and PBs with TPA moieties, and could be expected to open a new avenue of applications for PBs.